Thiosalicylic compound and process of making same.



UNITED s'ra ns r'rnr EDUARD MttNcH, or LUDWIGSHAFEN-ON-THE-RHI1\TE, ennivranxassreiion "To BADISCHE ANILIN & sons. FABRIK, or LUDWIGSHAFEN-QN-THE-RHINE, GERMANY,

A CORPORATION.

THIOSALICYLIC ooivrrounn AND rnoenss or MAKING No Drawing.

To all whom it may concern:

Be it known that I, EDUARD Murcia, doctor of philosophy and chemist, a subject of the Grand Duke of Baden. residing at Ludwi-gshafen-omthe-Rhine, .in the country of Germany, have invented new and useful Improvements in Thiosalicylic Conipounds and Processes of Making the me,

of which the following is a specification.

I have discovered that trichlorethylene, or

'tribromethylene, can be made to react on thiosalicylic acid compounds, thereby yield- 'ing compounds which, by suitable treatment, can condensed to form leuco compounds of thioindigo coloring matters. Under the term thiosalic'ilic acid compounds I include thiosalicylic acid itself and also homo logues and analoguesthereof and derivatives of any of these compounds, for instance dithiosalicylic' acid, sulfocyanbenzoic acid, xa-nthogen-benzoic acid, and the sulfurized benzoic acid derivatives, obtainable by-treating the corresponding ortho-diazobenzoic acid compounds with alkali polysulfid;

The reaction between trihalogen-ethylene and 'the thiosalicylioacid compound should always be carried out in the presence of sufficient metal to combine with at least one halogen atom of the trihalogen-cthylene employed'. This can be brought about for instance in the case of thiosalicylic acid itself by employing the potassium salt thereofgin which case the reaction can be represented by the equatlon'z R/SK I excess of free alkali above the quantity before stated be present. I term the co1n pounds so obtained omega-dihalogen-vinylthiosalicylic acid compounds.

,My new compounds are characterized by the following properties. They are colorless Specification of Letters Patent.

or onlv sliohtlv colored are easilysolublein FatentedJDeetidgjtgtlgli Application filed September 1, 1998. Serial ale. 451,250. 1'

alcohol and in benzene; more difiicultly soluble in ligroin and very ditiicultly-soluble in water. On treatment with an alkaline condensing agent they yield 'leuco compounds of thioindigo coloring matters. I do not, however, claim such production of leuco compounds in this application, since this forms the subjectmatter of Patent No. 910839, January 26, 19095 I The following examples will-serve to illus-' trate further the nature of my invention and how it can be carried into practicaleiiec-ti but it is not confined to these examples. The" parts are by weight. and the temperatures are given in degrees Centigrade. i

Example 1: Heat a solution ot'fifteen and -two-fifths (15.4) parts of thiosalicylic -acid and twelve and two-fifthstlZA) parts of caustic potash in fifty (:50) parts or" niethyl ated spirits on the water-bath, andadd' thirteen (13) parts of trichlorethylenei":Boil the whole for about eight (8') hours '11 a reflux apparatus, take up with water-and precipate with hydrochloric acid, whereu)on ome 'a-dichlor-vin l thiosalicwlic acid is obtained andcan be recrystallized from benzene, yielding colorless crystals i'vh-i'clr melt at one hundred and st 1'enty'th1."ee (173') degrees. t x

Example Heat a olution of thirtyeight and one-fifth (38.2) partsof potassiumdithiosalicylate and twelveand two-fifths" (12.4) parts of caustic potash in one hundred (190) parts of methylated spirits in reflux apparatus on the water-bath and-add,

slowly, drop by drop, twenty-six "parts of trichlorethylcne. Heat for from sixl(6),

to eight. (8) hours, distil oii the greater part of the methylated spirits, take up the residue with water and precipitate the omegadichlor-vinyl-th1osalicylic acid by means of .hvdrochloric acid.

Example 3: Heata solution of twentythree and three-tenths parts of parabrt.;nt-hiosalicylic acid in a quantity oi": alcoholic potash containing eleven and one-fifth (112) parts of caustic potash, on the waterbath, and add thirteen (13) parts of enchlorethylene. Then continue heating for several hours, dilute with water, and precipitate by means of hydrochloric acid. The omega-dichlor-vinyl-p ara brom-thiosahcyno acid can be recrystallized from benzene cipitate the omega-dichlor-vinyl-thiosalicylic acid by means of acid. 1

Example 5 Heat together in an autoclave, for three (3) hours, at from one'hundred and twenty (120), to one hundred and forty (140), degrees, forty-four (41) parts of the potassium salt of ethyl-thiosalicylate, one hundred (100) parts of alcohol, and twentyseven (27) parts of trichlorethylene. .Then distil off the alcohol and'extra'ct the ethyl ester of omega dichlor vinyl thiosalicylic acid from the residue by means of ether. The ester consists of a li' ht-brown'viscous oil and is easilysoluble'in alcohol and in benzene.

Example 6: Dissolve twentyeight and three-fifths (28.6) parts of 4-ethoxy-2- xanthogen benzoic acid in a solution of eighteen (18) parts of potassium hydroxid' in one hundred (100) parts of alcohol, addfourteen (14) parts of trichlorethylene andboil the whole in a reflux apparatus on the Water-bath for about four (4:) hours. Then add a little water and distil off the alcohol,

acidify the residue-filter off the precipitate and wash and dry it at a moderate temperature. On cr-ystallizing it frombenzene and ligroin, meta-=- ethoxy omega dichlor vinylthiosalicylic acid can he obtained as a light crystalline powder.

Example 7: Dissolve thirty and four-fifths I (30.8.) parts of thiosalicylic acid in eleven and lone-fifth (11.2) parts of potassium hydroxid and two hundred (200) parts of alcohol, and then add fifty (50) parts of tribromethyleireQ After a short time, reaction takes 5 4306 and the mixture beconiw mun.

Allov. a he mix! 11 re to stand for several hours. and ihen add water and hydrochloric acid,

whereupon omega dichroin vinyl thiosal i cylic acid is precipitated and can be ri-wrystallized from benzene.v

If, in the foregoing Example 6, seventeen and nine-tenths (17.9) parts of sulfocyanbenzoic acid be employed, instead of the 4- ethoxy 2 xantho'gen benzoic acid, omega dichlor-vinyl-thiosalicylic acid can be obtained.

Now what I claim is:

1. The process of producing omega-dihalogen-vinyl-thiosalicylic acid compounds by acting with trihalogenethylene on a hereinbefore defined thiosalicylic acid compound subst-antially as described.

2. The process of producing omega-dichlorvinyl-thiosalicylic acid by acting on thiosalicylic acid with .trichlorethylene in the presence of caustic potash.

3. As a new article of manufacture omegadihalogen-vinyl-thiosalicylic acid compounds Which can be obtained by acting with tridihalogen vinyhth'iosalicylic acid compounds thiosalicylic acid compound-Which new compounds are colorless or only slightly colored,

' are easil soluble in alcohol andinbenzen'e,

I cultly soluble in ligroin and very difiicultly' soluble in Water, and on treatment more di with an alkaline condensing agentyield leuco compounds of thioindigo coloring matters.

4. As a new article of manufacture omegadichlor-vinyl-thiosalicylic acid which consists of colorless crystals which melt at about 173 C., are easily soluble .in alcohol. and benzene, more difiicultly soluble in ligroin, very diflicultly soluble in water and on treat nient with an alkaline condensing. agent gives rise. to a leuco compound, of a thioindigo coloring matter;

-l n'testimony whereof I. have hereunto set my hand in the presence of two subscribing witnesses. I

EDUARD MUNCH. \Vitnesses (J. ALEc. LLOYD, RA. SIcsBnn. 

